Spinning solutions containing organic dyes and products thereof



Patented Jan. 31, 1939 UNITED STATES SPINNING SOLUTIONS ooNTAININo.ORGAN- 1o DYES AND PRODUCTS THEREOF Rudolph S. Bley, Milligan College,Tenn., assignor to North American Rayon Corporation, New York, N. Y., acorporation of Delaware No Drawing. Application October 13, 1934, Se-

rial No. 748,259. Renewed June 7, 1938 3 Claims.

The present invention relates to a process of producing dyed rayonproducts, such. as filaments, yarns, ribbons, films, etc., by admixingsuitable organic dyes with the spinning solutions prior to 5 theextrusion thereof.

The primary object of my invention has to do with the addition of suchorganic dyes to strongly alkaline spinning solutions, such as viscose,cuprammonium cellulose, silk fibroin, alkali metal alginates, gelatine,etc., which will not be deleteriously affected by alkali or acids,desulphurizing agents and bleaching compounds used in the manufacture ofartificial products from said spinning solutions.

Another object of this invention has to do with the incorporation ofTriazol-Echtrot C (Griesheim), Toluylenrot (Griesheim), Triazol-Reinblau R, etc., into strongly alkaline spinning solutions.

Other objects of my invention will become apparent to those skilled inthe art after a study of the following specification.

I am well aware that it has, heretofore, been proposed to add inorganicpigments to cellulosic spinning solutions with a view of formingtherefrom dyed products. However, until the present time, it has beenimpossible to incorporate organic dyes into strongly alkaline spinningsolutions without impairing the colors of the finished products. Viscoserayon, for example, is produced by treating cellulose with strongcaustic alkali to form alkali cellulose which, subsequently, istransformed into cellulose xanthogenate (viscose) with the assistance ofcarbon bisulphide. After 1 ripening the viscose solution, it is spuninto a sulphuric acid bath, etc., to form regenerated cellulose. Thesulphur is removed from the regenerated cellulose with alkalinesulphides, such as ammonium sulphide, etc. Finally the viscose 40products are bleached with sodium hypochlorite solutions, etc.

Cuprammonium cellulose is produced by dissolving cellulose in copperhydroxide-ammonia solution and spinning the dissolved cellulose intoacid or alkaline spinning baths. The products are then freed from copperand bleached. In a similar manner, artificial products are made fromalkaline solutions of alginates, silk fibroin, gelatine, etc. From theabove, it will readily be recog- 50 nized that only such organic dyescan be incorporated into alkaline spinning baths which are resistant toacids, desulphurizing agents and bleaching compounds, otherwisesatisfactory products cannot be obtained. It is for this reason thatrayon products have, heretofore, been exclusively dyed in finished form,i. e., after removal of sulphur, bleaching agents, etc. Unexpectedly,

I have found that a number of organic dyes, for

example Triazol-Echtrot C (Griesheim), To-

luylenrot (Griesheim) Triazol-Reinblau R,

etc. can be admixed with strongly alkaline spin ning solutions withoutbeing decomposed by the same. These dyes are manufactured by theChemische Fabrik Griesheim-Elektron in Germany and. sold under theaforementioned tradenames.

These dyestuffs have the following chemical structures:

(1) Triazol-Echtrot C (Grieslieim): O2eHinNn01SNai C 0 0 Na ITIH:

G. Schultz Farbstoiftabellen, VII edition, Vol. pp. 171, No. 410.

(2) Toluylenrot (Griesheim): Ca1H aNgOnS4Na4Clz OaNa Cl 1 G HzN S oaNBHaN S OaNfl Qnag S OaNa G Schultz arbstofftabellen", VII edition, Vol.I,

pp. '177, No. 425

(3) 'lriazol-Reinblau R (Grleshoim): o n monsmas G. SchultzFarbstoiftabellefl, VII edition, Vol. I, pp. 193, No. 469.

They may be dissolved and/or dispersed in alkaline spinning solutions toform therewith after extrusion uniformly dyed products. The proportionsof dye, added to the spinning solutions, may

be varied at will in order to produce any desired color-shade, and it ispossible to admix a plurality of different dyes with a single batch ofspinning solution. Instead of admixing the dyes with the whole bulk ofspinning solution before entering the spinning machines, it is advisableto strongly dye a portion of the spinning solution and to mix it withthe rest of spinning solution just before entering the spinningmachines.

Modifications of my invention will readily be recognized by thoseskilled in the art, and I wish to include all modifications fallingwithin the scope of the appended claims.

I claim:

1. A spinning solution for the manufacture of dyed artificial productscomprising a viscose solution and a dye of the group consisting ofTriazol- Echtrot C (Griesheim) having the formula C29H19N5O7SNa2,Toluylenrot (Griesheim) ,having the formula Cs2I-IisNeO12S4Na4Cl2 andTriazol-Reinblau R having the formula 2. A spinning solution for themanufacture of dyed artificial products comprising a cellulosic solutionof the group consisting of viscose and cuprammonium cellulose and anorganic dyestufi of the group consisting of Triazol-Echtrot C(Griesheim) having the formula C2sH19N5O7SNa2, Toluylenrot (Griesheim)having the formula C32H1sNsOi2S4Na4C'l2 and Triazol-ReinblauRlGriesheim) having the formula C34H24N5O11SsNa3.

3. A spinning solution for the manufacture of dyed artificial productscomprising a cuproammonium cellulose solution and a dye of the groupconsisting of Triazol-Echtrot C (Griesheim) having the formulaC29H19N5O7SNa2, Toluylenrot (Griesheim) having the formulaC32H18N6012S4N3AC12 and Triazol-Reinblau R having the formulaC34H24N5O11S3Na3.

RUDOLPH S. BLEY.

